CN109293909B - Preparation method of polyalkyl polyol polyoxyethylene ether - Google Patents
Preparation method of polyalkyl polyol polyoxyethylene ether Download PDFInfo
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- CN109293909B CN109293909B CN201810896571.6A CN201810896571A CN109293909B CN 109293909 B CN109293909 B CN 109293909B CN 201810896571 A CN201810896571 A CN 201810896571A CN 109293909 B CN109293909 B CN 109293909B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
Abstract
The invention discloses a preparation method of polyalkyl polyol polyoxyethylene ether, which comprises the following steps: adding alkyl glycol and ethylene glycol diglyceride into a reaction bottle, raising the temperature of the reaction bottle to a first set temperature, and uniformly stirring; adding a catalyst, and standing for a first set time; after the temperature is increased to a second set temperature, standing for a second set time; after the temperature is raised to a third set temperature, standing for a third set time to obtain polyalkyl polyol; adding polyalkyl polyol into an autoclave, and adding potassium hydride and dimethylethylamine; heating to a fourth set temperature, adding an alkoxylation reagent, and continuously reacting for a fourth set time; cooling and depressurizing to obtain the oxyalkylation reagent and the catalyst, thus obtaining the polyalkyl polyol polyoxyethylene ether. The polyalkyl polyol polyoxyethylene ether prepared by the preparation method has the characteristics of low foam, low surface tension, high wetting property, high permeability and the like, and is suitable for being used as a surfactant.
Description
Technical Field
The invention relates to the technical field of a synthesis method of a polyalkyl polyol nonionic surfactant, in particular to a preparation method of polyalkyl polyol polyoxyethylene ether.
Background
It is known that acetylene glycol polyoxyethylene ether nonionic surfactants have low dynamic surface tension and are widely applied to water-based coatings, inks, adhesives and pesticide emulsifiers to achieve a good wetting effect. Conventional nonionic surfactants, such as alkyl phenols or alcohol ethoxylates and Ethylene Oxide (EO) and Propylene Oxide (PO) copolymers have excellent equilibrium surface tension properties, often characterized by low dynamic surface tension reduction. In contrast, certain anionic surfactants such as sodium alkyl sulfosuccinate monoesters can provide good dynamic results, but these are highly foaming and the resulting films are susceptible to water attack. Although the triphenylphenol polyoxyethylene ether and the trialkylphenol polyoxyethylene ether have better pesticide emulsifying capacity, the toxicity of the parent bodies is unfavorable for organisms and environment, and the triphenylphenol polyoxyethylene ether and the trialkylphenol polyoxyethylene ether are only suitable for being used in the aspect of pesticide emulsification.
Disclosure of Invention
One object of the present invention is: provided is a process for producing a polyalkyl polyol polyoxyethylene ether which has low foaming, low surface tension, high wetting, high permeability and other properties and is suitable for use as a surfactant.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of polyalkyl polyol polyoxyethylene ether comprises the following steps:
adding alkyl glycol and glycol diglyceride into a reaction bottle,
raising the temperature of the reaction bottle to a first set temperature and then uniformly stirring;
adding a catalyst, and standing for a first set time;
after the temperature is increased to a second set temperature, standing for a second set time;
after the temperature is raised to a third set temperature, standing for a third set time to obtain polyalkyl polyol;
adding polyalkyl polyol into an autoclave, and adding potassium hydride and dimethylethylamine;
heating to a fourth set temperature, adding an alkoxylation reagent, and continuously reacting for a fourth set time;
cooling and depressurizing to obtain the oxyalkylation reagent and the catalyst, thus obtaining the polyalkyl polyol polyoxyethylene ether.
In a preferred embodiment, the first set time is 2 hours, the second set time is 1 hour, the third set time is 2 hours, and the fourth set time is 1.5 hours.
As a preferable technical solution, the first set temperature is 50 ℃, the second set temperature is 80 ℃, the third set temperature is 120 ℃, and the fourth set temperature is 60 ℃.
As a preferred technical scheme, the catalyst is boron trifluoride diethyl etherate.
In a preferred embodiment, the catalyst is one or more of alkali metal hydride, alkali metal hydroxide or trialkylamine.
In a preferred embodiment, the alkali metal hydride is potassium hydride or sodium hydride.
As a preferable technical scheme, the trialkylamine is trimethylamine, triethylamine, dimethylethylamine or tributylamine.
In a preferred embodiment, the alkoxylation agent is ethylene oxide or propylene oxide.
In a preferred embodiment, the diol in the alkanediol is 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 3, 5-dimethyl-1-hexyn-3-ol or 3, 6-dimethyl-1-heptyn-3-ol.
As a preferred technical scheme, the molar ratio of the alkyl diol to the glycol diglyceride ether is 1:1-10: 1.
The invention has the beneficial effects that: provided is a process for producing a polyalkyl polyol polyoxyethylene ether which has low foaming, low surface tension, high wetting, high permeability and other properties and is suitable for use as a surfactant.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In this embodiment, a method for preparing a polyalkyl polyol polyoxyethylene ether includes the following steps: adding alkyl glycol and ethylene glycol diglyceride into a reaction bottle, raising the temperature of the reaction bottle to a first set temperature, and uniformly stirring; adding a catalyst, and standing for a first set time; after the temperature is increased to a second set temperature, standing for a second set time; after the temperature is raised to a third set temperature, standing for a third set time to obtain polyalkyl polyol; adding polyalkyl polyol into an autoclave, and adding potassium hydride and dimethylethylamine; heating to a fourth set temperature, adding an alkoxylation reagent, and continuously reacting for a fourth set time; cooling and depressurizing to obtain the oxyalkylation reagent and the catalyst, thus obtaining the polyalkyl polyol polyoxyethylene ether.
The polyalkyl polyol of the invention is a low dynamic tension surfactant obtained by connecting a reactive monomer on the basis of an acetylenic diol to form a polyalkyl polyol precursor and alkoxylating and adding the polyalkyl polyol precursor. Due to their excellent surface activity and low foaming properties, such products can find applications in many fields where lower dynamic and equilibrium surface tensions and low foaming are important. These applications include in various wet-spinning processes, such as fiber dyeing, fiber fermentation and scouring, where low foam properties are most beneficial; they are also suitable for soaps, water-based perfumes, shampoos and various detergents. Low surface tension, and substantially no foam, would be very desirable, which is superior to the polyoxyethylene ethers made from their precursor acetylenic diols.
The alkyl diol is of the structure:
wherein R1 is methyl or hydrogen, and R2 is alkyl.
The polyalkyl polyol is obtained by reacting alkynediol and ethylene glycol diglyceride, and has the following structure:
the molar ratio of the glycol to the glycol diglyceride ether is more than or equal to 2:1, an alcohol head system (product in the reaction formula) mainly comprising a diad is obtained, if the ratio is equal to 1:1, the alcohol head of the high-molecular polyalkyl polyol is obtained, the performance difference of the alkoxylates prepared from the two alcohol heads is very large, and the application field is also greatly different. The application of the product of the invention is still the application field of the glycol ether, but the overall performance is better.
In this embodiment, the first setting time is 2 hours, the second setting time is 1 hour, the third setting time is 2 hours, and the fourth setting time is 1.5 hours.
In this embodiment, the first set temperature is 50 ℃, the second set temperature is 80 ℃, the third set temperature is 120 ℃, and the fourth set temperature is 60 ℃.
In this example, the catalyst was boron trifluoride etherate. The dosage of the compound is 0.1 to 2 percent of the total weight of the raw materials. More preferably 0.5%.
In this embodiment, the catalyst is one or more of an alkali metal hydride, an alkali metal hydroxide, or a trialkylamine.
In this embodiment, the alkali metal hydride is potassium hydride or sodium hydride. In other embodiments, the molar ratio of alkali metal hydride to alkylamine is from 1:5 to 1:20, more preferably 1: 10.
In this embodiment, the trialkylamine is trimethylamine, triethylamine, dimethylethylamine or tributylamine.
In this embodiment, the alkoxylating agent is ethylene oxide or propylene oxide. The alkoxylation temperature is from 30 ℃ to 150 ℃, more preferably from 45 ℃ to 130 ℃, most preferably from 55 ℃ to 65 ℃.
In this example, the diol in the alkyl diol is 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 3, 5-dimethyl-1-hexyn-3-ol, or 3, 6-dimethyl-1-heptyn-3-ol.
In this example, the molar ratio of the alkyl glycol to the ethylene glycol diglyceride ether was 10: 1.
The specific operation mode is as follows:
adding 238.3g (95%) of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 87g of ethylene glycol diglyceride into a 500ml four-necked flask equipped with a stirring motor, a thermometer, a reflux condenser and an electric heating jacket, heating to 50 ℃ under the protection of nitrogen, uniformly stirring, adding 1.7g of boron trifluoride diethyl etherate, stirring and reacting for 2 hours, slowly heating to 80 ℃ for reacting for 1 hour, slowly heating to 120 ℃ for reacting for 2 hours, slowly reducing the pressure, and evaporating the boron trifluoride diethyl etherate to obtain polyalkyl polyol;
163g of the polyalkyl polyol were charged into a 500ml autoclave and 5g (60%) of potassium hydride and 60g of dimethylethylamine. The reactor was sealed, replaced with 0.3MPa nitrogen three times, and heated to 60 ℃. Injecting ethylene oxide by nitrogen (control speed of a double-valve tube), wherein the reaction pressure is not more than 0.4MPa, the temperature is not more than 70 ℃, pressing 220g of ethylene oxide into the reaction kettle, and continuously reacting for 1.5 hours after the pressure is zero. And (3) cooling, removing the product, and evaporating unreacted ethylene oxide and the catalyst by using a three-neck flask under reduced pressure to obtain the polyalkyl polyol polyoxyethylene ether.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention and the technical principles used, and any changes or substitutions which can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the protective scope of the present invention.
Claims (9)
1. A preparation method of polyalkyl polyol polyoxyethylene ether is characterized by comprising the following steps:
adding alkynediol and ethylene glycol diglyceride ether into a reaction bottle, wherein the molar ratio of the alkynediol to the ethylene glycol diglyceride ether is more than or equal to 2:1,
raising the temperature of the reaction bottle to a first set temperature and then uniformly stirring;
adding a catalyst, and standing for a first set time;
after the temperature is increased to a second set temperature, standing for a second set time;
after the temperature is raised to a third set temperature, standing for a third set time to obtain polyalkyl polyol;
adding polyalkyl polyol into an autoclave, and adding potassium hydride and dimethylethylamine;
heating to a fourth set temperature, adding an alkoxylation reagent, and continuously reacting for a fourth set time;
cooling and depressurizing to obtain the oxyalkylation reagent and the catalyst, thus obtaining the polyalkyl polyol polyoxyethylene ether.
2. The method of claim 1, wherein the first set time is 2 hours, the second set time is 1 hour, the third set time is 2 hours, and the fourth set time is 1.5 hours.
3. The method of claim 1, wherein the first set temperature is 50 ℃, the second set temperature is 80 ℃, the third set temperature is 120 ℃ and the fourth set temperature is 60 ℃.
4. The process for preparing a polyalkylpolyol polyoxyethylene ether according to claim 1, wherein the catalyst is boron trifluoride etherate.
5. The method of claim 1, wherein the catalyst is one or more of alkali metal hydride, alkali metal hydroxide, or trialkylamine.
6. The process for preparing a polyalkyl polyol polyoxyethylene ether according to claim 5, wherein the alkali metal hydride is potassium hydride or sodium hydride.
7. The method of claim 5, wherein the trialkylamine is trimethylamine, triethylamine, dimethylethylamine or tributylamine.
8. The method of claim 1, wherein the diol in the alkynediol is 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 3, 5-dimethyl-1-hexyn-3-ol, or 3, 6-dimethyl-1-heptyn-3-ol.
9. The method of claim 1, wherein the molar ratio of the acetylenic diol to the ethylene glycol diglyceride is 1:1 to 10: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1477473A1 (en) * | 2003-05-14 | 2004-11-17 | Goldschmidt AG | Aminoalcohol based surfactants with reduced surface tension and the use thereof |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN103965462A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Catalyst for synthesis of acetylene alcohol polyoxyethylene ether |
| CN104557789A (en) * | 2015-01-22 | 2015-04-29 | 重庆艾克米科技有限公司 | Tertiary alkynediol glycidyl ether and derivatives thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1477473A1 (en) * | 2003-05-14 | 2004-11-17 | Goldschmidt AG | Aminoalcohol based surfactants with reduced surface tension and the use thereof |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN103965462A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Catalyst for synthesis of acetylene alcohol polyoxyethylene ether |
| CN104557789A (en) * | 2015-01-22 | 2015-04-29 | 重庆艾克米科技有限公司 | Tertiary alkynediol glycidyl ether and derivatives thereof |
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